CN102753661A - Antiwear composition and method of lubricating an internal combustion engine - Google Patents

Abstract

The present invention relates to a lubricating composition containing an oil of lubricating viscosity and an antiv/ear package. The antiwear package may contain a derivative of a hydroxycarboxylic acid; and a salt of a sulphur-free phosphorus-containing compound. The salt includes amine salts, ammonium salts, metal salts and mixtures thereof. The invention further provides for a method of supplying an internal combustion engine with the lubricating composition.

Description

The antiwear composite and the method for lubricated oil engine

Technical field

The invention provides the lubricating composition that contains wear-resistant suit.The invention further relates to the method for lubricating oil engine through with said lubricating composition lubricating engine.

Background technology

Manufacturers of engines has been devoted to improve engine design, to improve fuel economy and efficient (usually, based on Federal Corporate Average Fuel Economy (CAFE) standard) and to reduce wearing and tearing.Although engine design and operating improvement contribute, the improved prescription of engine oil lubricants also can reduce wear when improving fuel economy and efficient.They also help to reduce the friction between the slip movable part (usually metal or pottery) of contact.

Be well known that lubricating oil contains and is useful on the many additives (comprising anti-wear agent, inhibitor, dispersion agent or purification agent) that prevent that internal-combustion engine abrasion, oxidation, soot deposits and acid from gathering.The common wear preventive additive of engine oil is zinc dialkyl dithiophosphate (ZDDP).It is believed that the ZDDP wear preventive additive protects mover through on the metallic surface, forming protective membrane.ZDDP is considered to that also fuel economy and efficient are had harmful effect.Therefore, engine lubricant also can contain friction improver to eliminate the harmful effect of ZDDP to fuel economy and efficient.But ZDDP and friction improver all play a role on the sliding surface and interfere separately function each other separately through being adsorbed on.

In addition, the engine lubricant that contains phosphorus compound and sulphur has shown that part causes the discharging of particle emission and other pollutent.In addition, sulphur and phosphorus tend to poison catalyzer used in the catalytic converter, cause the performance of said catalyzer to reduce.

Along with discharge (common and promotion NO _xFormation, SO _xForm, sulfate ash forms and the efficient that reduces the aftertreatment catalytic converter is associated) control improve, hope to reduce the amount of sulphur, p and s acidifying ash content in the engine oil.Also be considered to volatile relatively and along with being about to introduce the GF-5 specification from the phosphorus of ZDDP, need be to the stricter restriction of phosphorus discharging.But the content that reduces wear preventive additive (for example ZDDP) possibly improve other harmful performance of wearing and tearing and causing mover.

In addition, along with technical progress, the component exposed of mover is under more harsh operational conditions.Operational conditions can comprise the use of more high power density mover, turbocharger, use of fuel substitute etc.Under many harsh operational conditionss, the wearing and tearing and/or the oxidation of lubricant and parts take place more easily.

USP 5,338,470 disclose the alkylation citric acid derivant as the reaction product acquisition of Hydrocerol A and alkyl alcohol or amine.This alkylation citric acid derivant is effectively as anti-wear agent and friction improver.

USP 4,237,022 discloses the additive that can be used as in lubricant and the fuel with effective reduction singing and friction and the tartaroyl imines that improves fuel economy.

USP 4,952,328 disclose the lubricating oil composition of oil engine, and its oil, (B) that comprises (A) lubricant viscosity is through the carboxylic acid derivative that makes the reaction of succinic acylating agent and some amine and process and (C) the alkaline alkali metal salt of sulfonic acid or carboxylic acid.

USP 4,326,972 disclose the lubricant compositions of the fuel economy that is used to improve oil engine.Said composition comprises specific vulcanising composition (based on carboxylicesters) and alkaline alkali metal sulphonate.

U.S. Patent application 60/862534 (PCT/US07/082057; Present US 2010-0048437) malonic ester that is suitable as anti-wear agent is disclosed.

International Publication WO 2005/087904 discloses the lubricant that contains hydroxycarboxylic acid and hydroxy polycarboxylic acid esters and phosphor-included additive.This phosphor-included additive comprises dialkyl zinc dithiophosphate and/or neutral phosphonic compound, like tricresyl phosphate lauryl or triphenyl thiophosphatephosphorothioate.This lubricant can be used for engine lubricant.

International Publication WO 2006/044411 discloses low-sulfur, low-phosphorous, the low ash lubricant composition that the ester that contains every carboxamido-group has tartrate or the acid amides of 1 to 150 carbon atom.This lubricant compositions is fit to lubricated oil engine.The not open as compsn disclosed herein of WO 2006/044411.

Summary of the invention

Contriver of the present invention has been found that; Lubricating composition disclosed herein and method can provide following at least one of acceptable level: (i) phosphorus discharging (reduce usually or prevent and discharge); (ii) sulphur emissions (reduce usually or prevent discharging); (iii) frictional behaviour and (iv) wearing and tearing and/or extreme pressure property (reduce usually or prevent).

In one embodiment, the invention provides the oil that comprises lubricant viscosity and the lubricating composition of wear-resistant suit, wherein said wear-resistant suit comprises:

(a) verivate of hydroxycarboxylic acid; With

(b) salt of no sulphur P contained compound.This salt comprises amine salt, ammonium salt, metal-salt and their mixtures.(" ammonium salt " comprises monoalkyl ammonium salt, dialkyl ammonium salt, trialkyl ammonium salts or tetraalkylammonium salt and unsubstituted ammonium salt.)

In one embodiment, because this wear-resistant suit, thereby can reduce or eliminate the amount of zinc dialkyl dithiophosphate wear preventive additive.

In one embodiment, the invention provides the oil that comprises lubricant viscosity and the lubricating composition of wear-resistant suit, wherein this wear-resistant suit comprises:

(a) anti-wear agent of formula (1a) and/or compounds represented (1b):

Wherein

N ' is 0 to 10 as far as formula (1b), is 1 to 10 as far as formula (1a);

P is 1 to 5;

Y and Y ' be independently-O-,＞NH,＞NR ³, through make in (1b) Y and Y ' group or (1a) in two Y groups form R together and between two＞C=O group ¹-N＜group and the imide group that forms;

X is-CH independently ₂-,＞CHR ⁴Or＞CR ⁴R ⁵,＞CHOR ⁶Or＞C (CO ₂R ⁶) ₂,-CH ₃,-CH ₂R ⁴Or-CHR ⁴R ⁵,-CH ₂OR ⁶,-CH (CO ₂R ⁶) ₂,＞C (OR ₆) CO ₂R ⁶,＞CHCO ₂R ⁶Or ≡ C-R ⁶(wherein ≡ equals trivalent, and can be only applicable to formula (1a)) or their mixture, with satisfy formula (1a) and/or valency (1b) (usually formula (1a) or compound (1b) have at least one hydroxyl X (for example,＞CHOR ⁶, R wherein ⁶Be hydrogen));

R ¹And R ²Be alkyl independently, contain the alkyl of 1 to 150,4 to 30 or 6 to 24 carbon atoms usually;

R ³It is alkyl;

R ⁴And R ⁵Be group (for example acyl group), ester group or the alkyl of ketone group containing independently; And

R ⁶Be hydrogen or alkyl independently, be generally the alkyl that contains 1 to 150 carbon atom; With

(b) salt of no sulphur P contained compound (it is normally oil-soluble).This salt comprises amine salt, ammonium salt, metal-salt and composition thereof.

Formula (1a) and/or compound (1b) can also be expressed from the next:

Wherein

N and m can be 1 to 5 integer independently;

X can be aliphatic series or alicyclic group, or in carbochain, contains the aliphatic series or the alicyclic group of Sauerstoffatom, or the substituted group of the above-mentioned type, and said group contains maximum 6 carbon atoms and has n+m the point that can supply connect;

Each Y can be independently-O-,＞NH or＞NR ¹Or two Y represent together the imide structure R-N that between two carbonyls, forms＜nitrogen; And

Each R and R ¹Can be hydrogen or alkyl independently, condition be at least one R or R ¹Group is an alkyl; Each R ²Can be hydrogen, alkyl or acyl group independently, condition further is at least one-OR ²Group be positioned at X at least one-α of C (O)-Y-R group or the carbon atom of β position on.

Derived from the compound of hydroxycarboxylic acid can derived from oxyacetic acid (n and m equal 1), oxysuccinic acid (n=2, m=1), tartrate (n and m equal 2), Hydrocerol A (n=3, m=1) or their mixture.In one embodiment, can be derived from the compound of hydroxycarboxylic acid derived from tartrate or oxyacetic acid, usually derived from tartrate.

In one embodiment, the verivate of hydroxycarboxylic acid comprises imide, diester, diamide or the ester-acid amide verivate of tartrate, Hydrocerol A or its mixture.In one embodiment, the verivate of hydroxycarboxylic acid comprises tartaric imide, diester, diamide or ester-acid amide verivate.

When the X hydroxyl, formula (1a) and/or compound (1b) can be derived from hydroxycarboxylic acids, for example tartrate, Hydrocerol A or its mixture.In one embodiment, formula (1a) and/or compound deriving (1b) are from Hydrocerol A and R ¹And R ²Contain at least 6 or at least 8 carbon atoms to 150 or 6 to 30 or 8 to 24 carbon atoms.In one embodiment, formula (1a) and/or compound deriving (1b) are from tartrate and R ¹And R ²Contain 4 to 30 or 6 to 24 carbon atoms.

As X not during hydroxyl, formula (1a) and/or compound (1b) can be derived from for example propanedioic acid, oxalic acid, chloro-phenyl-propanedioic acid or their mixtures.

In different embodiments, the component of said lubricating composition (b) can be the salt that is selected from by the no sulphur P contained compound of the no sulfur metal salt of the P contained compound of hydrocarbyl substituted and the group that the phosphorylation dispersion agent is formed.

In different embodiments, lubricating composition disclosed herein contains 0ppm to 1000ppm, 0ppm to 500ppm or 5ppm to 300ppm or 20ppm to 250ppm molybdenum.

In one embodiment, the invention provides the method for lubricated oil engine, comprise to mover supply such as lubricating composition disclosed herein.

In different embodiments; Contain the salt that has or not the sulphur P contained compound to the described lubricating composition of this method, the group that the substituted diester of phosphorylation hydroxyl of the no sulfur metal salt of the P contained compound of its optional free hydrocarbyl substituted, phosphorylation dispersion agent, the substituted phosphodiester of hydroxyl, phosphoric acid or salt or three esters and their mixture are formed.

In one embodiment; The invention provides purposes like lubricating composition disclosed herein; Be used to provide following at least one item of acceptable level: (i) phosphorus discharging (reduce usually or prevent and discharge); (ii) sulphur emissions (reduce usually or prevent discharging), (iii) frictional behaviour and (iv) wearing and tearing and/or extreme pressure property (reduce usually or prevent).

Detailed Description Of The Invention

The invention provides method like disclosed lubricating composition of preceding text and lubricated mechanism.This mechanism is oil engine normally.

Wear-resistant suit

Wear-resistant suit comprises two kinds or more kinds of like the disclosed anti-wear agent of preceding text.

This wear-resistant suit can exist with 0.01 weight % to 10 weight % of lubricating composition or 0.05 weight % to 10 weight % or 0.05 weight % to 5 weight %.

The verivate of hydroxycarboxylic acid (or anti-wear agent of formula (1a) and/or compounds represented (1b)) can exist with 0.005 weight % to 10 weight % of lubricating composition or 0.025 to 5 weight % or 0.25 to 2.5 weight %.

The anti-wear agent of formula (1a) and/or compounds represented (1b)

In one embodiment, the anti-wear agent of formula (1a) and/or compounds represented (1b) can be the verivate of hydroxycarboxylic acid.

In one embodiment, a kind of anti-wear agent comprises the verivate of hydroxycarboxylic acid.The verivate of hydroxycarboxylic acid is generally tartrate/salt, also can serve as rust-preventive agent and inhibiter, friction improver, anti-wear agent and emulsion splitter.In one embodiment, the verivate of hydroxycarboxylic acid also can have friction improvement character.

In one embodiment, the verivate of hydroxycarboxylic acid can be ashless, that is, the amount of institute's containing metal is not more than the amount relevant with amount of pollutant.

The verivate of hydroxycarboxylic acid comprises that imide, diester, diamide, imide (be applicable to tetracid and more higher acid), ester-acid amide, ester-imide (are applicable to three acid and higher acid more; Hydrocerol A for example) or imide-acid amides (be applicable to three acid with more higher acid, for example Hydrocerol A).In one embodiment, anti-wear agent comprises imide, diester, diamide or ester-acid amide.

In one embodiment; This anti-wear agent can (be applicable to three acid and higher acid more derived from hydroxycarboxylic acid diester, hydroxycarboxylic acid diamide, hydroxycarboxylic acid imide (be applicable to tetracid and more higher acid), hydroxycarboxylic acid ester-acid amide, hydroxycarboxylic acid esters-imide; Hydrocerol A for example) and in hydroxycarboxylic acid imide-acid amides (be applicable to three acid with more higher acid, for example Hydrocerol A) at least one.In one embodiment, anti-wear agent can be derived from least one in hydroxycarboxylic acid diester, hydroxycarboxylic acid diamide and the hydroxycarboxylic acid ester-acid amide.

The instance of suitable hydroxycarboxylic acid comprises Hydrocerol A, tartrate, oxysuccinic acid (or hydroxy succinic acid), racemic melic acid, lactic acid, oxyacetic acid, hydroxy-propionic acid, hydroxyl pentanedioic acid or their mixture.In one embodiment, anti-wear agent can be derived from tartrate, Hydrocerol A, hydroxy succinic acid, the acid of dihydroxyl list, monohydroxy diacid or their mixture.In one embodiment, anti-wear agent comprises derived from tartaric compound.

U.S. Patent application 2005/198894 discloses suitable hydroxy carboxylic acid compound and preparation method thereof.

Canadian Patent 1183125; U.S. Patent Publication 2006/0183647 and US-2006-0079413; Patent Application No. 60/867402 (PCT/US07/085547); The instance of suitable tartaric acid derivatives is all disclosed with English Patent 2105743A.

At USP 4,237, the detailed description (through making tartrate and primary amine reaction) for preparing the suitable imido method of winestone is disclosed in 022.

In one embodiment, anti-wear agent comprises tartaric imide, diester, diamide, ester-acid amide verivate.

In one embodiment, anti-wear agent can be by above-mentioned formula (1a) and/or compounds represented (1b):

Wherein

N ' is 0 to 10,0 to 6 or 0 to 4 as far as formula (1b), is 1 to 4 or 1 to 2 as far as formula (1a);

P is 1 to 5, or 1 to 2, or 1;

Y and Y ' be independently-O-,＞NH,＞NR ³, or through make Y and Y ' group form R together and between two＞C=O group ¹-N＜group and the imide group that forms;

X is-CH independently ₂-,＞CHR ⁴Or＞CR ⁴R ⁵,＞CHOR ⁶Or＞C (CO ₂R ⁶) ₂,-CH ₃,-CH ₂R ⁴Or CHR ⁴R ⁵,-CH ₂OR ⁶,-CH (CO ₂R ⁶) ₂,＞C (OR ₆) CO ₂R ⁶,＞CHCO ₂R ⁶Or ≡ C-R ⁶(wherein ≡ equals trivalent, and can be only applicable to formula (1a)) or their mixture, with satisfy formula (1a) and/or valency (1b) (usually formula (1a) or compound (1b) have at least one hydroxyl X (promptly＞CHOR ⁶, R wherein ⁶Be hydrogen));

R ¹And R ²Be alkyl independently, contain 1 to 150,4 to 30 or 6 to 20 or 10 to 20 or 11 to 18 carbon atoms usually;

R ³It is alkyl;

R ⁴And R ⁵Be ketone group, ester group or alkyl independently; With

R ⁶Independently for hydrogen or alkyl, contain the alkyl of 1 to 150 or 4 to 30 carbon atom usually.

In one embodiment; Diester, diamide, imide (be applicable to tetracid and more higher acid), ester-acid amide, ester-imide (are applicable to three acid and higher acid more; Hydrocerol A for example), compound can be derived from formula (1a) and/or compound (1b) for imide-acid amides (be applicable to three acid with more higher acid, for example Hydrocerol A).In one embodiment, diester, diamide, the ester-acid amide compound can be derived from formula (1a) and/or compound (1b).

In one embodiment, the compound of formula (1b) contains imide group.This imide group is usually following to be formed: make in (1b) Y and Y ' group or (1a) in two Y groups form R together and between two＞C=O group ¹-N＜group.

In one embodiment, formula (1a) and/or compound (1b) have n, X and the R as giving a definition ¹, R ²And R ⁶: n is 1 to 2, and X is＞CHOR ⁶And R ¹And R ²Be the alkyl that contains 4 to 30 carbon atoms independently, and R ⁶Be hydrogen or the alkyl that contains 4 to 30 carbon atoms independently.

In one embodiment, Y and Y ' are-O-.

In one embodiment, formula (1a) and/or compound (1b) have n, X, Y, Y ' and the R as giving a definition ¹, R ²And R ⁶: n is 1 to 2, and X is＞CHOR ⁶Y and Y ' are-O-, and R ¹And R ²Be the alkyl that contains 4 to 30 carbon atoms independently, and R ⁶Be hydrogen or the alkyl that contains 4 to 30 carbon atoms independently.

Can come preparation formula (1a) and/or diester (1b), diamide, imide (be applicable to tetracid with more higher acid), ester-acid amide, ester-imide (to be applicable to three acid and higher acid more through randomly in the presence of known esterifying catalyst, making poly carboxylic acid (for example tartrate) and amine or alcohol reaction; Hydrocerol A for example), imide-acid amides (be applicable to three acid with more higher acid, for example Hydrocerol A) compound.This amine or alcohol have usually to be enough to satisfy suc as formula (1a) and/or the R (1b) ¹And/or R ²The carbon atom of requirement.

In one embodiment, R ¹And R ²Can be the straight or branched alkyl independently.In one embodiment, this alkyl can be a side chain.In one embodiment, this alkyl can be a straight chain.R ¹And R ²Can through amine or alcohol incorporate into formula (1a) and/or (1b) in.This alcohol comprises monohydroxy-alcohol and polyvalent alcohol.In one embodiment, this alcohol is side chain.

In one embodiment, this anti-wear agent can be derived from the compound of formula (1b).

The instance of suitable branched-chain alcoho comprises 2-Ethylhexyl Alcohol, different tridecyl alcohol, Guerbet alcohol or their mixture.

The instance of monohydroxy-alcohol comprises methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, hendecanol, dodecanol, tridecyl alcohol, tetradecanol, pentadecylic alcohol, cetyl alcohol, heptadecanol, Stearyl alcohol, nonadecanol, EICOSANOL or their mixture.In one embodiment, monohydroxy-alcohol contains 5 to 20 carbon atoms.

This alcohol comprises monohydroxy-alcohol or polyvalent alcohol.Suitable examples of polyhydric alcohols comprises terepthaloyl moietie, Ucar 35,1; 3-butyleneglycol, 2; 3-butyleneglycol, 1,5-pentanediol, 1,6-pinakon, glycerine, Sorbitol Powder, tetramethylolmethane, TriMethylolPropane(TMP), starch, glucose, sucrose, methyl glucoside or their mixture.In one embodiment, polyvalent alcohol can be mixed together use with monohydroxy-alcohol.Usually, in this combination, monohydroxy-alcohol constitutes at least 60 moles of % or at least 90 moles of % of this mixture.

In one embodiment, anti-wear agent can be derived from tartrate.The tartrate that is used to prepare tartrate/salt of the present invention (for example can be buied; Available from Sargent Welch); It can exist with one or more isomeric forms, for example d-tartrate, l-tartrate, d, l-tartrate (racemic mixture) or mesotartaric acid; Usually depend on source (natural) or compound method (for example, by toxilic acid).These verivates also can be by function coordinator (for example ester, chloride of acid or the acid anhydride) preparation of the conspicuous diacid of those skilled in the art.

When formula (1a) and/or compound deriving (1b) during from tartrate, according to the certain alcohols that is used to prepare this tartrate/salt, gained tartrate/salt can be solid, semisolid or oily.For as the additive in the oleaginous composition (comprise lubricated and fuel composition), this tartrate/salt is advantageously solvable and/or can stably be dispersed in this type of oleaginous composition.For example, but to be used in the normally oil-soluble and/or stable dispersion of compsn in the oil in the oil that will use them.Used term " oil-soluble " is meant that not necessarily all said compsns all can be miscible under all proportions or be soluble in all oil in this specification sheets and the appended claims; And be meant that said composition is making solution show oil-soluble on the degree of one or more required character (for example MO or synthetic oil, said composition will play a role) in this oil.Similarly, this type " solution " needs not to be the true solution on strict physics or the chemical sense.They can be microemulsion or colloidal dispersion, and these show enough character near true solution for the purpose of the present invention, thereby see in the context of the present invention and can exchange with them from practical standpoint.

The salt of no sulphur P contained compound

The group that the optional free following substances of the salt of no sulphur P contained compound is formed: the no sulfur metal of the P contained compound of hydrocarbyl substituted or amine salt, phosphorylation dispersion agent, the substituted phosphodiester of hydroxyl, the substituted phosphodiester of phosphorylation hydroxyl or three esters and their mixture.

The amine salt of P contained compound

In one embodiment, the amine salt of no sulphur P contained compound can be the salt of following substances: (i) the substituted phosphodiester of hydroxyl, or (ii) substituted phosphodiester of phosphorylation hydroxyl or three esters.The amine salt of no sulphur P contained compound can be represented by formula (2):

Wherein

A and A ' are H or the alkyl that contains 1 to 30 carbon atom independently;

Each R and R " group is alkyl independently;

Each R ' is R, H or hydroxyalkyl independently;

Y is R ' or RO (R ' O) P (O)-CH (A ') CH (A)-(RO (R ' O) P (O)-CH for example independently ₂CH (CH ₃Group shown in)-);

X ' is 0 to 1 (in one embodiment, when x '=0, R ' is a hydroxyalkyl); And

M and n are positive nonzero integers, and condition is that (m+n) sum equals 4;

M is a metals ion;

T is the integer of 1 to 4 (or 1 to 2); And

Q and e are marks, and their summation provides the combination without repetition that satisfies t valency, and condition is that q is 0.1 to 1.5 (or 0.1 to 1), and e is 0 to 0.9.

The amine salt of no sulphur P contained compound can be represented by formula (2a):

Wherein

A and A ' are H or the alkyl that contains 1 to 30 carbon atom independently;

Each R and R " group is alkyl independently;

Each R ' is R, H or hydroxyalkyl independently;

Y is R ' or RO (R ' O) P (O)-CH (A ') CH (A)-(RO (R ' O) P (O)-CH for example independently ₂CH (CH ₃Group shown in)-);

X ' is 0 to 1 (in one embodiment, when x '=0, R ' is a hydroxyalkyl);

M and n are positive nonzero integers, and condition is that (m+n) sum equals 4.

In one embodiment, the compound shown in formula (2) or the formula (2a) has and equals 1 x '.

In one embodiment, the compound shown in formula (2) or the formula (2a) has and equals 0 x '.

In one embodiment, the compound shown in formula (2) or the formula (2a) has and equals 2 m; With the n that equals 2.

In one embodiment, the compound shown in formula (2) or the formula (2a) has and equals 3 m; With the n that equals 1.

In one embodiment, A and A ' contain 1 to 10 or 2 to 6 or 2 to 4 carbon atom independently.

In one embodiment, R, R ' and R " all contain 1 to 30 or 1 to 20 or 4 to 20 carbon atom independently.In one embodiment, half the at most R ' group can be a hydrogen.

In one embodiment, R " contain 8 to 26 or 10 to 20 or 13 to 19 carbon atoms.

In one embodiment, when x ' equaled 0, the compound of formula (2) or formula (2a) can be like USP 6,468, disclosed phosphamide in 946.Wherein disclosed phosphamide can be single alkyl or the substituted ester of dialkyl with the salifiable phosphorus compound of amine.The ester group of each hydrocarbyl substituted can contain 4 to 40 or 6 to 20 carbon atoms.

At USP 6,468, the instance of suitable compound is also disclosed among 946 the embodiment P-4 to P-8 (referring to paragraph [0060] to [0064]).Also can use other alcohol, comprise the saturated or unsaturated alcohol that contains 12 to 15 or 16 to 18 or 20 to 24 carbon atoms, repeat USP 6,468, the reaction of describing among 946 the P-4 to P-8.Available alcohol is C ₁₈Alcohol.

The compound of formula (2) or formula (2a) comprises the amine salt of primary amine, secondary amine, tertiary amine or its mixture.In one embodiment, this primary amine comprises uncle's aliphatic primary amine.

The instance of suitable primary amine comprises ethamine, propylamine, butylamine, 2-DEHA, octylame and lauryl amine, and like the aliphatic amide of n-octylamine, positive decyl amine, dodecyl amine, n-tetradecane base amine, n-hexadecyl amine, Octadecane base amine and oily enamine and so on.Other available aliphatic amide comprises commercially available aliphatic amide; For example

amine (can be available from Akzo Chemicals; Chicago; The product of Illinois); For example Armeen C, Armeen O, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD, wherein letter names relate to fat group, for example cocoyl, oleyl, tallow base or stearyl.

The instance of suitable secondary amine comprises n n dimetylaniline; Diethylamine; Dipropyl amine; Dibutylamine; Diamylamine; Dihexylamine; Two heptyl amices; Methylethyl amine; N-Ethylbutylamine; Two-the 2-DEHA; N-methyl isophthalic acid-amino-hexanaphthene; 2C and ethyl pentyl group amine.This secondary amine can be cyclammonium, for example piperidines, piperazine and morpholine.

The instance of tertiary amine comprises three-n-butylamine, three-n-octylamine, three-decyl amine, three-laurylamine, three-hexadecylamine, three-2-DEHA and diformazan base oil enamine (

DMOD).

In one embodiment, amine can be form of mixtures.The instance of suitable amine mixt comprises that (i) contains the amine of 11 to 14 carbon atoms on tertiary alkyl uncle group, (ii) on tertiary alkyl uncle group, contains the amine of 14 to 18 carbon atoms, or (iii) on tertiary alkyl uncle group, contains the amine of 18 to 22 carbon atoms.Other instance of primary t-alkyl-amine comprises TERTIARY BUTYL AMINE, uncle's hexylamine, tert-Octylamine (for example 1; The 1-dimethylhexylamine), uncle's decyl amine (as 1,1-dimethyl-octylame), uncle's lauryl amine, uncle's tetradecylamine, uncle's hexadecylamine, uncle's octadecylamine, uncle's tetracosyl amine and uncle's octacosyl amine.

In one embodiment, the available amine mixt comprises "

81R " or "

JMT ".

81R and JMT (by manufactured and sold by Rohm & Haas) are C11 to C14 tertiary alkyl primary amines, C18 to C22 tertiary alkyl primary amine mixture.

In one embodiment, the metals ion of formula (2) can be unit price or divalent metal or its mixture.In one embodiment, this metals ion can be a divalence.

In one embodiment, the metal of this metals ion comprises lithium, sodium, potassium, calcium, magnesium, barium, copper, nickel, tin or zinc.

In one embodiment, the metal of this metals ion comprises lithium, sodium, calcium, magnesium or zinc.In one embodiment, the metal of this metals ion can be a zinc.

In one embodiment, when the compound of formula (2) was the metal-salt of amine salt or monovalence metal, t equaled 1.

In one embodiment, when the compound of formula (2) was the metal-salt of divalent metal, t equaled 2.

In one embodiment, q is 0.5 to 1; And e is 0 to 0.5.

In one embodiment, the compound of formula (2) not metal ion (e equals 0; And q equals 1).

In one embodiment, t equals 1, e equal 0 and q equal 1.

The method of the compound of preparation formula (2) and formula (2a)

In one embodiment, make amine and (i) the substituted phosphodiester of hydroxyl or the (ii) method of the substituted phosphodiester of phosphorylation hydroxyl or the reaction of three esters, obtain maybe can obtain the no thiamines salt of P contained compound through comprising.

In one embodiment, through comprising that the method that makes amine and (i) the substituted phosphodiester of hydroxyl or the (ii) substituted phosphodiester of phosphorylation hydroxyl or the reaction of three esters obtains maybe can obtain the no thiamines salt of P contained compound.

In one embodiment, the salt of the substituted phosphodiester of hydroxyl can prepare through the method that comprises the steps:

(i) make phosphoric acid agent (P for example ₂O ₅, P ₄O ₁₀Or its coordinator) with the alcohol reaction, to form phosplate and/or bisphosphate;

(ii) make the reaction of this SULPHOSUCCINIC ACID ESTER and oxirane, to form the substituted phosphodiester of hydroxyl; With

(iii) through making the substituted phosphodiester salify of this hydroxyl with amine and/or metal reaction.

In one embodiment; With amine and/or metal salify (as above-mentioned step (iii) in) before; Through repeating above-mentioned steps (i), can make (ii) substituted phosphodiester of hydroxyl and the further reaction of phosphoric acid agent (form the substituted phosphodiester of hydroxyl or three esters of phosphorylation usually) at least again.

In different embodiments, with amine and/or metal salify (as above-mentioned step (iii) in) before, step (i) and (ii) can repeating is at least again carried out step (i) after randomly.For example, can be through comprising the step (i) that as above defines, (ii) and (iii); Or (i), (ii), (i) and (iii); Or (i), (ii), (i), (ii) and (iii); (i), (ii), (i), (ii), (i) and (iii); Or (i), (ii), (i), (ii), (i), (ii) and (iii); Or (i), (ii), (i), (ii), (i), (ii), (i) and (iii), or (i), (ii), (i), (ii), (i), (ii), (i), (ii) and this salt of the preparation of method (iii).

In different embodiments, reaction product provides the no thiamines salt of the P contained compound of the present invention of 1 weight % to 99 weight % or 20 weight % to 80 weight % or 35 weight % to 75 weight %.

In different embodiments, the mol ratio of phosplate and bisphosphate comprises the scope of 1: 10 to 10: 1 or 1: 5 to 5: 1 or 1: 2 to 2: 1 or 1: 1 in step (i).

In different embodiments, in step (i) mol ratio (based on the amount of phosphorus) of the phosplate of oxirane and step (i) and/or bisphosphate comprise 0.6: 1 to 1.5: 1 or 0.8: 1 to 1.2: 1, comprise 1: 1 scope.

In one embodiment, oxirane comprises oxyethane, propylene oxide or butylene oxide ring; The mol ratio of (ii) middle oxirane of step and the substituted phosphodiester of hydroxyl comprises 1: 1.

In one embodiment, oxirane comprises C ₅More senior oxirane; And the mol ratio of (ii) middle oxirane of step and the substituted phosphodiester of hydroxyl comprises more wide region, because oxirane is more non-volatile under reaction conditions.

In different embodiments, preceding text can carry out in the temperature of reaction of 30 ℃ to 140 ℃ or 40 ℃ to 110 ℃ or 45 ℃ to 90 ℃ in the method for step (i) description in (iii).

Said method can or be higher than under the normal atmosphere at decompression, normal atmosphere carries out.In one embodiment, said method can or be higher than under the normal atmosphere at normal atmosphere and carries out.

In one embodiment, said method can be carried out in inert atmosphere.The instance of suitable inert atmosphere comprises nitrogen, argon or its mixture.

In different embodiments, oxirane contains 2 to 10 or 2 to 6 or 2 to 4 carbon atoms.In one embodiment, oxirane comprises oxyethane, propylene oxide, butylene oxide ring or its mixture.In one embodiment, oxirane comprises propylene oxide.

In different embodiments, said alcohol contains 1 to 30 or 4 to 24 or 8 to 18 carbon atom.This alcohol can be straight or branched.This alcohol can be saturated or undersaturated.

The instance of suitable alcohol comprises hexanol, enanthol, octanol, nonyl alcohol, dodecanol, tridecyl alcohol, tetradecanol, pentadecylic alcohol, cetyl alcohol, heptadecanol, Stearyl alcohol, octadecenyl alcohol (oily enol), nonadecanol, EICOSANOL or their mixture.The instance of suitable alcohol comprises for example 4-methyl-2-amylalcohol, 2-Ethylhexyl Alcohol, isooctyl alcohol or their mixture.

Examples of commercially available alcohols include Monsanto, Oxo 7911, Oxo

7900 and Oxo

1100; ICI's

79; Condea (now Sasol) of 1620,

610 and

810; Ethyl? Corporation's

610 and 810; Shell? AG's

79,

911 and 25L; Condea? Augusta, Milan's

125; Henkel? KGaA (now Cognis) of

and

and Ugine? Kuhlmann's 7-11 and

91.

Available amine comprises the amine salt of primary amine, secondary amine, tertiary amine or its mixture.The more detailed description of available amine can see above.

The amine salt that can prepare phosphoric acid through the method for describing among the International Publication WO 2008/094759.Especially, preparation example 1 to 4 has been described in paragraph [0151] to [0158].

The no sulfur metal salt of the P contained compound of hydrocarbyl substituted

In one embodiment, the salt of no sulphur P contained compound is known, and can be like disclosed such preparation in EP287618, USP 2,228,658, USP 4,431,552 and the USP 2,310,175.The instance of the salt of wherein disclosed no sulphur P contained compound comprises the phosphorous acid metal-salt of the phosphonic acid metal salt of hydrocarbyl substituted, the hypophosphorous acid metal salt of hydrocarbyl substituted (phosphinate), hydrocarbyl substituted, the phosphonous acid metal-salt of hydrocarbyl substituted, the metal phosphinate (phosphinite) or their mixture of hydrocarbyl substituted.

In one embodiment, the phosphorus atom of the P contained compound of this hydrocarbyl substituted is a pentavalent.

In one embodiment, the no sulfur metal salt of the P contained compound of hydrocarbyl substituted is the substituted phosphonate of metal alkyl or its mixture.

The phosphorylation dispersion agent

In one embodiment, the salt of no sulphur P contained compound is the phosphorylation dispersion agent.The phosphorylation dispersion agent can be through making inorganic phosphorus acid or anhydride and nitrogenous dispersion agent react and prepare.Gained phosphorylation dispersion agent it is believed that the amine salt that forms nitrogenous dispersion agent, and counter ion are derived from phosphoric acid agent.This nitrogenous dispersion agent is normally ashless.The reaction of preferably guaranteeing acid or anhydride and the nitrogenous dispersion agent of said inorganic phosphorus produced make phosphorus incorporate in the dispersion agent and product but not form soluble phosphorus particulate.If the formation solia particle, then products therefrom maybe be muddy and unstable.Use this product possibly reduce observed effect through the present invention.

Ashless dispersant is usually known not to contain into grey metal before in being blended in lubricating oil composition, and they do not contribute any grey metal that becomes usually in adding lubricant and polymeric dispersant to the time.Ashless dispersant is characterised in that the polar group that is connected with the hydrocarbon chain of higher molecular weight.

The instance of acid or anhydride of inorganic phosphorus that can be used for forming the salt of no sulphur P contained compound comprises phosphorous acid, phosphoric acid (H ₃PO ₄), diphosphanetetroic acid, phosphorus trioxide (P ₂O ₃), phosphorus tetroxide (P ₂O ₄) and phosphoric anhydride (P ₂O ₅Or P ₄O ₁₀).In one embodiment, the acid or anhydride of this inorganic phosphorus can be phosphorous acid (H ₃PO ₃) or phosphoric acid (H ₃PO ₄).

This is inorganic, the acid of oil soluble phosphorated can be reacted with the ashless dispersant that contains basic nitrogen or one or more free hydroxyl groups.Products therefrom it is believed that it is oil-soluble.This nitrogenous dispersion agent comprises: (i) succinimide of hydrocarbyl substituted; (ii) use the mixed ester/acid amides of the hydrocarbyl substituted succinic that alkanol, amine and/or aminoalkanol process; (iii) mannich dispersant, it is that the condensation product of phenol, formaldehyde and the polyethylene polyamine of hydrocarbyl substituted (is described in USP 3,368,972; 3,413,374; 3,539,633; 3,649,279; In 3,798,247 and 3,803,039); (iv) their mixture.

Typical ashless dispersant comprises the substituted long chain alkenyl succinimides of N-.The instance of the substituted long chain alkenyl succinimides of N-comprises polyisobutenyl succinimide, and wherein the substituent number-average molecular weight of polyisobutene is 350 to 5000,500 to 3000 or 550 to 2500.For example at USP 3,172,892 or USP 4,234,435 and in EP 0355895, disclose succinimide dispersants and preparation thereof.The imide that succinimide dispersants is normally formed by polyamines, common many (ethyleneamines).

In one embodiment, the present invention comprises that further at least a is the dispersion agent of 350 to 5000,500 to 3000 or 550 to 2500 polyisobutenyl succinimide derived from number-average molecular weight.This polyisobutylene succinimide can be united use separately or with other dispersion agent.

The oil of lubricant viscosity

Lubricating composition comprises the oil of lubricant viscosity.This type of oil comprises oil that natural and synthetic oil, hydrogen cracking, hydrogenation and unifining produces, unpurified, purified, the oil of re-refining, or their mixture.The more detailed description of the oil that unpurified, purified is provided in International Publication WO2008/147704 paragraph [0054] to [0056] and has re-refined.In the paragraph [0058] to [0059] of WO2008/147704, described natural respectively and more detailed description ucon oil.

Can make synthetic oil through fischer-tropsch reaction, and can be the Fischer-Tropsch hydrocarbon or the wax of hydroisomerization usually.In one embodiment, oil can and be other natural gas synthetic oil through the preparation of Fischer-Tropsch natural gas synthetic oil synthesis program.

The oil of lubricant viscosity also can be like in April, 2008 version of " Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils ", that kind definition of regulation in the 1.3rd joint subtitle 1.3 " Base Stock Categories ".In one embodiment, the oil of this lubricant viscosity can be API I class or II class or III class or IV class oil.In one embodiment, the oil of this lubricant viscosity can be API II class or III class oil.

The amount of the oil of lubricant viscosity normally deducts the summation surplus afterwards of the amount of compound of the present invention and other performance additive from 100 weight %.

This lubricating composition can be enriched material and/or full formula lubricant form.If lubricating composition of the present invention (comprising the disclosed additive of preceding text) is enriched material (it can merge to form finished lubricants wholly or in part with an additional oil) form, these additives and lubricant viscosity oily and/or comprise by weight 1: 99 to 99: 1 with the ratio of thinning oil or 80: 20 to 10: 90 scope by weight.

Other performance additive

Optional other performance additive that comprises of said composition.These performance additive are that the technician is known.This performance additive comprises metal passivator; Viscosity modifier (the hydrogenated copolymer of styrene butadiene for example; Ethylene-propylene copolymer or its mixture); Purification agent (salicylate/ester for example; Sulphonate/ester; Salixarates; Phenates/ester or its mixture); Friction improver (for example XU 61518.10); Anti-wear agent (for example zinc dialkyl dithiophosphate); Inhibiter; Dispersion agent (being generally succinimide); Dispersant viscosity modifiers; Extreme pressure agent; Inhibitor (comprises that alkylated diphenylamine (is generally dinonyldiphenylamine; Octyl diphenylamine; Dioctyl diphenylamine); Hindered phenol; Soluble molybdenum compounds; Or their mixture); Suds suppressor; Emulsion splitter; Pour point reducer; Sealing swelling agent and composition thereof.Usually, full formula lubricating oil contains in these performance additive one or multinomial.

In one embodiment, this lubricating composition further comprises in viscosity modifier, inhibitor, high alkaline detergent, succinimide dispersants (non-phosphorylation dispersion agent of the present invention), anti-wear agent (those that describe as a part of the present invention among non-this paper) or its mixture one or multinomial.

In one embodiment, this lubricating composition does not contain the dialkyl zinc dithiophosphate.In one embodiment, this lubricating composition further comprises the dialkyl zinc dithiophosphate.

In one embodiment; Hindered phenol antioxidant is an ester; And can comprise for example from the IrganoxTM L-135 of Ciba or derived from 2; The adduct of 6-di-tert-butylphenol and alkyl acrylate, wherein said alkyl can contain 1 to 18 or 2 to 12 or 2 to 8 or 2 to 6 or 4 carbon atom.The suitable more detailed description that contains ester hindered phenol antioxidant chemistry is found in USP 6,559,105.

In one embodiment, lubricating composition further contains soluble molybdenum compounds.This molybdenum compound can have the functional performance of anti-wear agent, inhibitor, friction improver or its mixture.Usually, this soluble molybdenum compounds comprises amine salt, xanthogenic acid molybdenum, moly-sulfide, carboxylic acid molybdenum, pure molybdenum or their mixture of molybdenum dithiocarbamate, molybdenum dialkyl-dithiophosphate, molybdenum compound.Moly-sulfide comprises molybdenumdisulphide.In one embodiment, this soluble molybdenum compounds is a molybdenum dithiocarbamate.

The suitable instance that can be used as the molybdenum dithiocarbamate of inhibitor comprises the Co. by R.T.Vanderbilt, and Ltd. is with trade(brand)name such as Molyvan 822 ^TMAnd Molyvan ^TMA sell and by Asahi Denka Kogyo KK with Adeka Sakura-Lube ^TMCommercial materials that S-100, S-165, S-515 and S-600 sell and composition thereof.

Industrial application

In one embodiment, said mechanism is an oil engine.

In one embodiment, said oil engine can be oil motor, petrol motor, natural gas engine or blend gasoline/pure mover.In one embodiment, this oil engine can be an oil motor, is petrol motor in another embodiment.

This oil engine can be double stroke or Otto cycle engine.Suitable oil engine comprises marine diesel, aviation piston type engine, underload oil motor, automobile and truck engine.

In one embodiment, this oil engine contains aluminium alloy part.This duraluminum comprises pure aluminium silicate, aluminum oxide or other stupalith.In one embodiment, this duraluminum is the pure aluminium silicate surface.

The lubricant compositions that is used for oil engine is applicable to any engine lubricant, and is irrelevant with sulphur, phosphorus or sulfate ash (ASTM D-874) content.The oil-contg of engine oil lubricants can be 1 weight % or lower, or 0.8 weight % or lower, or 0.5 weight % or lower, or 0.3 weight % or lower.In one embodiment, sulphur content can be 0.001 weight % to 0.5 weight %, or 0.01 weight % to 0.3 weight %.Phosphorus content can be 0.2 weight % or lower, or 0.1 weight % or lower, or 0.085 weight % or lower, or even 0.06 weight % or lower, 0.055 weight % or lower, or 0.05 weight % or lower.In one embodiment, phosphorus content can be 100ppm to 1000ppm, or 200ppm to 600ppm.Total sulfation ash oontent can be 2 weight % or lower, or 1.5 weight % or lower, or 1.1 weight % or lower, or 1 weight % or lower, or 0.8 weight % or lower, or 0.5 weight % or lower.In one embodiment, sulfate ash content can be 0.05 weight % to 0.9 weight %, or 0.1 weight % to 0.2 weight % to 0.45 weight %.

In one embodiment; Said lubricating composition is an engine oil; Wherein this lubricating composition is characterised in that and has (i) 0.5 weight % or lower sulphur content, (ii) 0.07 weight % or lower phosphorus content and (iii) 1.5 weight % or lower sulfate ash content.

In one embodiment, this lubricating composition is applicable to double stroke or four-stroke marine diesel oil oil engine.In one embodiment, the marine diesel oil oil engine is a two-stroke engine.

Wear-resistant suit can contain formula (1a) and/or the compound (1b) (or in one embodiment, the verivate of hydroxycarboxylic acid) of amount of 0.005 weight % to 10 weight % or 0.025 to the 5 weight % or 0.25 to the 2.5 weight % of this lubricating composition in internal combustion engine lubricant.

Wear-resistant suit can contain the salt of no sulphur P contained compound of amount of 0.005 weight % to 10 weight % or 0.025 to the 5 weight % or 0.25 to the 2.5 weight % of this lubricating composition in internal combustion engine lubricant.

The present invention of the following example illustration.These embodiment are not exhaustive, and are not in order to limit scope of the present invention.

Embodiment

Preparation Comparative Examples 1 (PCE1): the amine salt of the phosphorylation hydroxy alkyl ester of thiophosphoric acid: added Vanadium Pentoxide in FLAKES (144 gram) branch to 1176 at a distance from 1 hour for two parts and restrain O, in O-two (4-methyl-2-amyl group) the phosphorodithioic acid hydroxypropyl acrylate (preparing) through making two (4-methyl-2-amyl group)-phosphorodithioic acid and about 1.1 moles of propylene oxide react and remove excessive propylene oxide through coupling vacuum stripping at 54 ℃.This mixture is heated 6 hours to produce acid intermediate (1320 gram) at 71 ℃.Through added 555 gram C in 2 hours at 49 ℃ of warps _12-14Alkylamine, said midbody neutralizes.After being heated to 77 ℃, with this material coupling vacuum stripping to obtain product.

Engine oil lubricants (CE1 to CE4 and EX1 to EX2)

Embodiment 1 (EX1)Be internal combustion engine lubricant, its contain (i) 0.9 weight % with USP 6,468, the phosphamide that the similar mode of the P-4 described in 946 is processed, different is, and used alcohol is C18 alcohol, (ii) C ₆To C ₁₅Diester tartaric acid used and (iii) other conventional engine oil additive of alcohol comprises inhibitor, viscosity modifier, succinimide dispersants, XU 61518.10 friction improver, suds suppressor, pour point reducer and high alkaline detergent.This lubricant contains about 500ppm phosphorus.

Embodiment 2 (EX2)Be similar to embodiment 1, the product of the different above-mentioned preparation examples 1 that is to use 0.64 weight %.This lubricant contains about 500ppm phosphorus.

Comparative Examples 1 (CE1)Be similar to embodiment 2, different is that the product that will prepare example 1 changes the material of being processed by PCE1 into.This lubricant contains about 500ppm phosphorus.

Comparative Examples 2 (CE2)Be similar to embodiment 1, different is that this lubricant does not contain C ₆To C ₁₅Pure is diester tartaric acid used.This lubricant contains about 500ppm phosphorus.

Comparative Examples 3 (CE3)The product that contains the PCE1 of (i) 0.59 weight %; (ii) other conventional engine oil additive comprises inhibitor, viscosity modifier, succinimide dispersants, XU 61518.10 friction improver, suds suppressor, pour point reducer and high alkaline detergent.This lubricant contains about 500ppm phosphorus.

Comparative Examples 4 (CE4)Contain the product that (i) uses the above-mentioned preparation example 1 of 0.64 weight %; (ii) other conventional engine oil additive comprises inhibitor, viscosity modifier, succinimide dispersants, XU 61518.10 friction improver, suds suppressor, pour point reducer and high alkaline detergent.This lubricant contains about 500ppm phosphorus.

Use the reciprocal trier of high frequency (HFRR) to evaluate and test the wearing and tearing of each embodiment and Comparative Examples.Handle each sample with 1 weight % cumene hydroperoxide.The HFRR condition that is used to evaluate and test is 500 gram loads, 75 minute time length, 1000 microns strokes, 20 hertz frequencies and distribute at 105 ℃ isothermal.Measure then with the micron and be the polishing scratch of unit and be that the film of unit forms that low polishing scratch value and higher film formation value show improved polishing machine with the % film thickness.

The % film thickness is based on the measurement of the electromotive force between upper and lower metallographictest plate among the HFRR.When film thickness is 100%, in the total length of 1000 microns strokes, there is noble potential, showing does not have the intermetallic contact.On the contrary, under 0% film thickness, do not have electromotive force, the intermetallic contact that is illustrated between the plate is uninterrupted.Under intermediate film thickness, there is certain electromotive force, show that upper and lower metallographictest plate has intermetallic contact to a certain degree and other zone that does not have the intermetallic contact.The gained result is:

Embodiment	Polishing scratch (μ m)	Film thickness (%)
			EX1	304	36
EX2	159	85
			CE1	405	2
CE2	400	3
			CE3	388	2
CE4	401	2

In general, the result shows that the lubricating composition of the salt that contains (i) tartrate and (ii) do not have the sulphur P contained compound can form for oil engine provides the polishing machine of acceptable level and film.

The comparison of EX1 and EX2 and CE5

Embodiment C E5 is a lubricant compositions; It contains (i) known commercially available zinc dialkyl dithiophosphate (ZDDP) that is used in the internal combustion engine lubricant; (ii) other conventional engine oil additive comprises inhibitor, viscosity modifier, succinimide dispersants, XU 61518.10 friction improver, suds suppressor, pour point reducer and high alkaline detergent.This lubricant contains about 500ppm phosphorus.In HFRR, evaluate and test CE5 with aforesaid similar fashion.The result that CE5 is obtained shows 260 microns polishing scratch and 29% film thickness.Relatively CE5 and EX2 show that lubricant of the present invention (EX2) compares the wearing and tearing with reduction and the film thickness of raising with the lubricant that contains conventional ZDDP.Relatively CE5 and EX1 show that lubricant of the present invention (EX1) has the performance near the lubricant of the commercially available ZDDP of containing.In addition, EX1 has the film thickness formation of comparing raising with CE5.

In a word, EX2 has the improved performance than CE1 to CE5 aspect the film thickness formation of wearing and tearing reduction and raising.All improve to CE4 aspect the film thickness that EX1 reduces and improves in wearing and tearing than Comparative Examples CE1.In addition, EX1 does not have near the polishing machine of CE5 and need use ZDDP.

Embodiment 3 to 4 and Comparative Examples 6

Embodiment 3 (EX3)Be similar to EX1, the different 1 weight % butyl citrate replaced C that are to use ₆To C ₁₅Pure is diester tartaric acid used.

Embodiment 4 (EX4)Be similar to EX2, the different 1 weight % butyl citrate replaced C that are to use ₆To C ₁₅Pure is diester tartaric acid used.

Comparative Examples 6 (CE6)Be similar to CE1, the different 1 weight % butyl citrate replaced C that are to use ₆To C ₁₅Pure is diester tartaric acid used.

In HFRR, evaluate and test EX3, EX4 and CE6 with aforesaid similar fashion.The HFRR wear results that EX3, EX4 and CE6 are obtained is respectively 412 μ m, 397 μ m and 404 μ m.The film thickness result that EX3, EX4 and CE6 are obtained is respectively 2%, 2% and 3%.

Embodiment E X5 to EX6 and Comparative Examples CE7

The preparation of phosphorylation dispersion agent 1 (DP1): single succinimide dispersants of in flask, packing into (TBN=100,570 grams).This flask is warming up to 120 ℃ and use nitrogen purging.Dropwise added H through 1 hour ₃PO ₄(85%, 39 gram).This flask was warming up to 155 ℃ and vigorous stirring 5 hours.Add zeyssatite (25 gram) and filtration product and cooling, produce brown oil (511 gram).

The preparation of phosphorylation dispersion agent 2 (DP2): single succinimide dispersants of in flask, packing into (TBN=100,570 grams).This material is warming up to 110 ℃ and use nitrogen purging.With solid H ₃PO ₃(27 gram) is dissolved in the water (27 gram), and this solution was dropwise added in these goods through 1 hour.This flask was warming up to 155 ℃ and vigorous stirring 5 hours.Add zeyssatite (25 gram) and filtration product, produce darkorange oil (488 gram).

Embodiment 5 (EX5)Be the 5W-30 lubricant, it contains the product of (i) 2.8 weight %DP1, (ii) the C of 1 weight % ₆To C ₁₅Diester tartaric acid used and (iii) other conventional engine oil additive of alcohol comprises inhibitor, viscosity modifier, succinimide dispersants, XU 61518.10 friction improver, suds suppressor, pour point reducer and high alkaline detergent.This lubricant contains about 500ppm phosphorus.

Embodiment 6 (EX6)Be similar to EX5, the product of the different DP2 that is to use 2.3 weight % replaces DP1.This lubricant contains about 500ppm phosphorus.

Comparative Examples 7 (CE7)Be similar to EX5, different is the diester tartaric acid used of its C6 to C15 alcohol that does not contain 1 weight %.

Use the wearing and tearing of the reciprocal trier of high frequency (HFRR) through aforesaid method evaluation and test embodiment E X5 to EX6 and Comparative Examples CE7.The gained result is:

Embodiment	Polishing scratch (μ m)	Film thickness (%)
			EX5	170	49
EX6	174	44
			CE7	416	4

In general, the result show contain (i) tartrate and (ii) the lubricating composition of phosphorylation dispersion agent can form for oil engine provide polishing machine and the film of acceptable level.

Be known that more above-mentioned materials possibly interact in end formulation, so that the component of final preparation possibly be different from initial interpolation those.The product that forms thus is included in the product that forms when using lubricant compositions of the present invention in its desired use, may not simply describe.But modification that all are such and reaction product all comprise within the scope of the invention; The present invention includes the lubricant compositions of processing through mixing said ingredients.

Each document mentioned above is quoted through this and is incorporated this paper into.Except in an embodiment or showing clearly separately the part, specify all numerical quantities of quantity of material, reaction conditions, molecular weight, carbonatoms etc. should be understood that to modify in this specification sheets with word " approximately ".Only if indicate separately, each chemical or compsn that this paper mentions should be considered to the commercial grade material, and it possibly contain isomer, by product, verivate and be understood that to be present in other the such material in this commercial grade usually.But only if indicate separately, the amount of each chemical composition comprises conventional any solvent or the thinning oil that exists in the commercial materials.It being understood that the listed upper and lower bound amount of this paper, scope and ratio boundary can make up independently.Similarly, the scope of each key element of the present invention can be used with the scope or the amount of any other key element with amount.

Term used herein " hydrocarbyl substituent " or " alkyl " use well known to a person skilled in the art its its ordinary meaning.Particularly, it is meant and has carbon atom that directly is connected with the rest part of molecule and the group with the character that is mainly hydrocarbon.The instance of alkyl comprises: hydrocarbon substituent comprises aliphatic series, alicyclic and aromatic substituent; Substituted hydrocarbon substituent promptly contains the substituting group of the non-hydrocarbyl group that under situation of the present invention, does not change this substituent character that is mainly hydrocarbon; With assorted substituting group, promptly have the character that is mainly hydrocarbon similarly but in ring or chain, contain the substituting group of non-carbon-based group.The more specific definition of term " hydrocarbyl substituent " or " alkyl " has been described in the paragraph [0118] to [0119] of International Publication WO2008147704.

Explain the present invention although got in touch its preferred embodiment, it being understood that its various modifications are that those skilled in the art are conspicuous after reading specification sheets.Therefore, it being understood that the disclosed the present invention of this paper is intended to contain this type of modification in the scope that drops on appended claims.

Claims (18)

1. the lubricating composition of claim 1, wherein said composition comprises the oil and the wear-resistant suit of lubricant viscosity, and wherein this wear-resistant suit comprises:

(a) anti-wear agent of formula (1a) and/or compounds represented (1b):

(b)

Wherein

N ' is 0 to 10 as far as formula (1b), is 1 to 10 as far as formula (1a);

P is 1 to 5;

Y and Y ' be independently-O-,＞NH,＞NR ³, or imide group, said imide group through make in (1b) Y and Y ' group or (1a) in two Y groups form R together and between two＞C=O group ¹-N＜group and forming;

X is-CH independently ₂-,＞CHR ⁴Or＞CR ⁴R ⁵,＞CHOR ⁶, or＞C (CO ₂R ⁶) ₂,-CH ₃,-CH ₂R ⁴Or-CHR ⁴R ⁵,-CH ₂OR ⁶,-CH (CO ₂R ⁶) ₂,＞C (OR ₆) CO ₂R ⁶,＞CHCO ₂R ⁶, or ≡ C-R ⁶Or their mixture is to satisfy formula (1a) and/or valency (1b);

R ¹And R ²Independently for containing the alkyl of 1 to 150 carbon atom;

R ³It is alkyl;

R ⁴And R ⁵Be group, ester group or the alkyl of ketone group containing independently; And

R ⁶Independently for hydrogen or alkyl, contain the alkyl of 1 to 150 carbon atom usually; With

(b) salt of no sulphur P contained compound.

2. the lubricating composition of claim 1, the salt that does not wherein have the sulphur P contained compound is selected from the group of being made up of amine salt, ammonium salt, metal-salt and composition thereof.

3. each lubricating composition of aforementioned claim 1 to 2 does not wherein have the dispersion agent that the sulphur P contained compound is a phosphorylation.

4. each lubricating composition of aforementioned claim 1 to 3, the dispersion agent of wherein said phosphorylation is nitrogenous dispersion agent, is selected from the group of being made up of following substances:

(i) succinimide of hydrocarbyl substituted;

(ii) use the mixed ester/acid amides of the hydrocarbyl substituted succinic that alkanol, amine and/or aminoalkanol process;

(iii) mannich dispersant, it is the condensation product of phenol, formaldehyde and the polyethylene polyamine of hydrocarbyl substituted; With

(iv) their mixture.

5. the lubricating composition of claim 4, wherein said nitrogenous dispersion agent is a polyisobutenyl succinimide, wherein the substituent number-average molecular weight of polyisobutene is 500 to 3000, or 550 to 2500.

6. each lubricating composition of aforementioned claim 1 to 5, its Chinese style (1a) and/or compound (1b) are the verivates of hydroxycarboxylic acid.

7. each lubricating composition of aforementioned claim 1 to 6, the hydroxycarboxylic acid of the group that the free free tartrate of wherein X hydroxyl, and formula (1a) and/or compound deriving (1b), Hydrocerol A and composition thereof are formed.

8. each lubricating composition of aforementioned claim 1 to 7, wherein X hydroxyl, and formula (1a) and/or compound deriving (1b) are from tartrate.

9. each lubricating composition of aforementioned claim 1 to 8, its Chinese style (1a) and/or compound (1b) are tartaric imide, diester, diamide or ester-acid amide verivate.

10. each lubricating composition of aforementioned claim 1 to 5, wherein X hydroxyl not, and formula (1a) and/or compound deriving (1b) are from propanedioic acid, oxalic acid, chloro-phenyl-propanedioic acid or their mixture.

11. each lubricating composition of aforementioned claim 1 to 10, its Chinese style (1a) and/or compound (1b) exist with 0.025 to 5 weight % of this lubricating composition or the amount of 0.25 to 2.5 weight %.

12. each lubricating composition of aforementioned claim 1 to 11, the salt that does not wherein have the sulphur P contained compound exists with 0.025 to 5 weight % of this lubricating composition or the amount of 0.25 to 2.5 weight %.

13. the method for lubricated oil engine comprises to mover and supplies aforementioned claim 1 to 12 each lubricating composition.

14. the method for claim 13, wherein this oil engine is double stroke or Otto cycle engine.

15. each method of aforementioned claim 13 to 14, wherein said lubricating composition has (i) 0.5 weight % or lower sulphur content, (ii) 0.07 weight % or lower phosphorus content and (iii) 1.5 weight % or lower sulfate ash content.

16. each method of aforementioned claim 13 to 15, wherein said lubricating composition has the sulphur content of 0.001 weight % to 0.5 weight % or 0.01 weight % to 0.3 weight %.

18. lubricating composition comprises the oil and the wear-resistant suit of lubricant viscosity, wherein this wear-resistant suit comprises:

(a) verivate of hydroxycarboxylic acid; With

(b) salt of no sulphur P contained compound.

19. the lubricating composition of claim 18, wherein the verivate of hydroxycarboxylic acid is the verivate of tartrate, Hydrocerol A or its mixture.